Metal resinates and method of preparation



Patented Uni.

METAL RESINATES AND METHOD OF PREPARATION William E. St. Clair and Ray V. Lawrence, New Orleans, La., assignors to the United States of America as represented by the Secretary of Agriculture No Drawing.

Application July 11, 1950,

Serial No. 173,223

(Granted under the act of March 3, 1883, as amended April 30, 1928; 370 O. G. 757) 33 Claims.

This application is made under the act of March 3, 1-883, as amended by the act of April 30, 1928, and the invention herein described, if patented in any country, may be manufactured and used by or for the Government of the United States of America for governmental purposes throughout the world without the payment to us of any royalty thereon.

This invention relates to new and improved metal resinates and to methods for their preparation. It also relates to improved metal resinates prepared from the condensation products of rosin materials, such as rosin derivatives, and rosin-containing materials with an aldehyde.

This invention is a continuation in part of applications, Serial No. 82,268, Serial No. 152,267, and Serial No. 152,268, all now abandoned.

We have found that novel and improved metal resinates may be prepared by reacting rosin or rosin derivative, an aldehyde and a source of a metal. The various modes of reaction and the variations in type of reactants will be explained in detail below.

The metal resinates prepared according to our invention are generally characterized by creased metal content, conchoidal fracture, and improved solubility in low solvency hydrocarbons. Our products are moreover generally more stable to heat and air, compared with prior metal resinates.

By metal we mean any of those elements considered to be metals in the Periodic Chart of the Elements which appears in General Chemistry," 5th edition (1944) by H. G. Deming, published by John Wiley and Sons, Inc.

The rosin material employed in our invention includes gum rosin, wood rosin, pine oleoresin, material containing rosin or rosin acids such as pine gum, heat-treated rosin, stabilized rosin such as disproportionated rosin, partially hydrogenated or partially dehydrogenated rosin. and polymerized or partially polymerized rosin. It also includes such materials as decarboxylated rosin, rosin oil, tall oil, esters of the rosin acids, such as methyl abietate, ester gum, vacuum strippings from rosin reactions, or any rosin-containing material which will react with an aldehyde under the conditions of our process as described herein. Metal resinates may be prepared from any of these rosins, rosin-containing material, or rosin derivatives in accordance with our invention.

The aldehydes may be lower aliphatic aldehydes such as formaldehyde, acetaldehyde, and the like, carbocyclic or heterocyclic aldehydes such as benzaldehyde or furfural, or higher aliphatic aldehydes such as heptaldehyde, stearic aldehyde, and the like. The wide variety of aldehydes which may be employed is illustrated in the specific examples and tables which appear below. In general, substituted or unsubstituted aldehydes of from one to eighteeen carbon atoms are suitable. The aldehydes may be used in the form of gases, liquids or solids, and may be either linear or cyclic polymers of aldehydes such as paraformaldehyde, paraldehyde, or any polymer or compound which will yield an aldehyde under the conditions of our invention such as methylal, acetal, etc., aqueous solution of aldehydes and other compounds which yield aldehydes on heating or other compounds in which an aldehyde is released either before or during the course of the reaction. aldehyde-yielding material as used in this application includes physical properties of the metal resinates obtained from rosin material and different aldehydes vary somewhat, yet all our resinates are generally characterized by the increased metal content, conchoidal fracture, an improved solubility as noted previouly.

The metal source may be the metal oxide, hydroxide, carbonate, basic carbonate, metal salt of organic or inorganic acids such as the formats, lactate, acetate, basic acetate; or in some cases the finely divided metal may be used.

The properties of the metal resinates when they are formed will be influenced to some extent by the kind and amount of the particular metal compounds used in preparation. If an acid resinate is desired, for example, we prefer to start with a rosin material which has been reacted with 5% or less of an aldehyde. For essentially neutral metal resinates or for those which contain more metal than can be accounted for by the number of carboxyl groups present, we prefer to employ a rosin material which has been reacted with more than 5% of an aldehyde, and to add more aldehyde as necessary.

Within the broad scope of our invention, the properties of the particular metal resinates will vary somewhat, depending upon the proportion and kind of reactants and the particular mode of carrying out the reaction. For instance, the color of the metal resinates is generally light, yet some are characterized by darker color than the rest. This darker color characterizes the metal resinates using formaldehyde. The various combinations of metal source, aldehyde and rosin material and variations in proportion of these The expression the aldehyde itself. The

ingredients lead to a wide range of products. It is to be understood, however that within these possible combinations there are rarely specific combinations which fail to produce resinates or which produce resinates not having the properties of metal content, fracture and solubility previously noted. These exceptions are, nevertheless few in number and do not detract materially from the operability of our broad method or the value of our broad class of products.

Our resins have the unique property of high solubility in the low solvency hydrocarbons, such as petroleum naphtha. These novel resins may be used as protective coatings, catalytic drying agents for unsaturated vegetable oil, fungicides. insecticides, bactericides, wood preservatives, surface undercoatings, mildewproofing agents, rustproofing agents, wetting and dispersing agents, lubricating agents, waterproofing agents, catalysts, glazing ceramics, etc. Other and further important advantages of our resinates will become apparent from the following descriptions and examples.

The aldehyde may be reacted with rosin in several different ways. The amount of aldehyde giving the desired effects may vary from 0.01% to 30% based on the weight of the rosin material used.

A product that usually gives very satisfactory resinates may be formed by mixing the rosin and from 1% to 5% aldehyde together and heating to about 120 to 230 C. or higher without agitation. In cases where resinates of maximum metal content are desired, it may be advantageous to add more aldehyde as the metal compound is added. In some cases it may be advantageous to mix the aldehyde with the metal compound and add the mixture slowly to the hot rosin. Another method of preparation is to add the aldehyde to the molten metal resinate. In most cases. it is advantageous to form the rosin-aldehyde reaction product first and to react this product with suitable metal compounds to form the metal resinate or mixed metal resinate. However, suitable resinates were prepared by mixing all the ingredients together and heating the mixture with or without mechanical agitation until the aldehyde refluxed, and then removing volatile substances from the reaction mixture, as necessary.

The rosin and aldehyde may be combined in a closed vessel under pressures greater than atmospheric. Such products may contain higher amounts of aldehyde than those reacted at atmospheric pressures. While metal resinates prepared from these products of high aldehyde content are usually less soluble in the low solvency hydrocarbon solvents than similar products prepared at atmospheric pressure, these resinates usually have better resistance to oxidation than.

resinates of low aldehyde content. It may also be advantageous to carryout the preparation 01 these resinates under an inert atmosphere. The rosin-aldehyde reaction product may be saponifled with aqueous sodium hydroxide and the deof a catalyst. However, satisfactory products were also prepared by using an acid to catalyze the rosin-aldehyde reaction.

While the reaction of rosin and an aldehyde may be carried out in the presence of acetic acid and this product reacted with a suitable metal compound, the product formed in this manner is dissimilar to that product which is formed by the reaction of rosin and an aldehyde with a metal acetate. The rosin-aldehyde-acetic acid-metal compound product is usually not as soluble in the low boiling petroleum hydrocarbons as the rosinaldehyde-metal acetate reaction product.

The process herein described may be applied generally to include the products which may result when rosin or pine gum containing one or more of the resin acids, or stabilized rosin, such as disproportionated rosin, partially hydrogenated or partially dehydrogenated rosin are treated with a suitable metal compound in conjunction with, prior to, or subsequent to the reaction with an aldehyde.

Also, the process as herein described may be applied generally to include the products which may result when rosin oil, tall oil, or esters of the resin acids, such as methyl abietate, ester gum, etc., are treated with a suitable metal compound in conjunction with, prior to, or subsequent to the reaction with an aldehyde. However, the products obtained by using these derivatives of rosin may vary widely in melting point, solubility, and other physical and chemical properties, etc., from those obtained with rosin.

In referring to metal resinates having a high metal content, we do not mean to limit ourselves to acid or even neutral metal resinates, but also to include products containing more metal than that required to react completely with the free carboxyl groups present. When we refer to the properties of these metal resinates, we refer to the property of the materials as a whole. This is done to avoid any controversy over whether the metal resinate itself or the concomitant impurities are responsible for the observed properties.

The metal acetate is a convenient source of the metal to use in the preparation of these products, but other forms of the metal, such as the metal oxide, hydroxide, formate,. lactate, carbonate, basic acetate, basic carbonate, or in some cases the finely divided metal may be used, as noted previously.

One technique that was found to be effective for some of the less active metal compounds (such as molybdenum oxide, tungsten oxide, and bismuth subcarbonate) was to make a slurry of the metal compounds in glacial acetic acid, and add the slurry slowly to the hot rosin-aldehyde reaction product. It was also found helpful in several cases to use the freshly precipitated hydroxide or basic carbonate of. some of the less active metals in glacial acetic acid prior to reaction with the rosin-aldehyde reaction product. In all cases where the acetate of the metal was available or could be formed a satisfactory metal resinate could be prepared.

Since the metals below hydrogen in the electromotive series usually form resinates that have lower decomposition temperatures than the metals above hydrogen it is necessary to carry out the preparation of such resinates at temperatures well below their decomposition point. When such resinates are prepared from the metal salt of a volatile carboxylic acid such as an acetate, it is usually desirable to remove the excess volatile acid by sparging with stem or an inert gas or by vacuum stripping.

Also, the choice of metal compound used to react with the rosin-aldehyde reaction product will influence the physical characteristics of the metal resinate. For instance, in preparing lead resinates if the basic lead carbonate is used the lead resinate prepared will be intermediate in color, high in melting point and solubility, whereas, if lead acetate is used the lead resinate will be lighter in color, lower in melting point and less soluble. These differences are apparent when the physical characteristics of the appended examples are compared at equivalent metal concentrations.

In order to avoid decomposition, it is usually desirable to prepare the resinates of such metals as copper or mercury at temperatures of the order of 100 to 130 C. while manganese resinates that have been heated at 400 C. for 30 minutes were still clear, homogeneous solids with softening points above 100 C.

If higher concentrations of volatile liquid aldehydes are desired, the reaction may be carried out in a closed reaction vessel under pressure to prevent loss of the aldehyde, or the entire reaction may be carried out under pressure greater than atmospheric, if desired.

Reactions involving more than 5% of a volatile aldehyde may be carried out in a closed reaction yessel under pressure, or in a vessel equipped with a reflux condenser. In this manner the metal compound can be added to the rosin-aldehyde mixture and the whole of the reactants refluxed until the reaction is completed. In some cases it is advantageous to remove some of the more volatile components after the reaction is completed. This can be accomplished by the usual methods, such as sparging with steam, sparging with an inert gas, or by vacuum stripping.

While the products prepared by our method are in some respects similar to some of the present metal resinates, there is considerable differ ence in many of their physical and chemical properties. These products prepared with an aldehyde show much greater solubility in the low solvency hydrocarbons, such as petroleum naphtha, than is shown by metal resinates prepared in the absence of an aldehyde.

We have found that mixtures of the aldehydes may be used advantageously to modify the rosin for the preparation of these metal resinates. In many cases the resinates obtained from the mixed aldehyde gave color grades better than those obtainable from either aldehyde used alone.

The properties of these metal resinates may also be varied to a considerable extent by using mixtures of two or more difierent metal compounds. For example, the melting point of zinc resinate may be increased by substituting equivalent amounts of calcium hydroxide for a part of the zinc oxide.

Solution stability, particularly with the common drier metals (cobalt, lead and manganese), may be obtained by the preparation of a single resinate containing a mixture of the desired metals.

In general, as the metal content of a particular resinate is increased, the melting point is increased and the color of the product is darkened. The color is darker with some aldehydes and with some metal compounds than with others.

The following are among the variables that influence the physical and chemical characteristics of the various metal resinates.

1. Kind of aldehyde used.

2. Concentration of aldehyde used.

3. The particular metal used.

4. The individual salt of a particular metal used.

5. Concentration of metal used.

6. The type of rosin or rosin derivative used.

7. Reaction temperature.

8. Reaction time.

The metal resinates prepared by our method have improved solubility characteristics in the common varnish solvents, such as petroleum naphtha, turpentine, mineral spirits, aromatic type solvents, and terpene hydrocarbons.

The rates of solution of the resinates listed in the examples were determined by crushing approximately 2 grams of the resinate to pass an eight-mesh screen and adding the required amount of solvent at room temperature and determining the time required to dissolve the sample by shaking on an automatic shaking machine.

Our invention is advantageous in that our method permits the preparation of metal resinates which are difficult if not impossible to prepare by prior methods for preparing resinates. For example, in the known reaction of rosin with metal compounds to form metal resinates, the reaction apparently proceeds in the expected manner with the formation of a metal abietate or in some cases to form a mixed salt, such as the metal acetate-abietate, and in either case the metal content obtainable appears to be limited by the number of carboxyl groups available. However, we have discovered that such rosin derivatives as methyl abietate, ester gum, decarboxylated rosin, or rosin oil, having acid numbers of less than 20, when reacted with an aldehyde, would react with a suitable metal compound, such as the metal acetate to yield a clear, homogeneous, refusible metal resinate completely soluble in the ordinary varnish solvents. Likewise, when the higher molecular weight aldehydes are incorporated into rosin they produce metal resinates of improved color and solubility compared to the metal resinates prepared using formaldehyde. Liquid decarboxylated rosin with an acid number of less than 20, when reacted with 5% of benzaldehyde gave a product which contained more metal than could be accounted for by the reaction of the carboxyl groups with the metal compound to form either the metal diabietate, or the mixed abietate-acetate. The reaction must therefore proceed by a different mechanism than it does in the case of the rosinmetal compounds prepared in the absence of an aldehyde.

It is known that some metal compounds, wher. reacted with rosin, frequently set into a semicrystalline infusible mass at concentrations of the metal far short of that which would theoretically neutralize the acid present in the rosin. Some of these products cannot be liquefied at temperatures below their decomposition point. When the reaction is carried out in a petroleum solvent, greater amounts of the metal compound may be added without blocking" or gelling" of the solution, but when the solvent is distilled from the reaction product, a semi-crystalline,

tlye in the presence of an aldehyde, this tendency to block is avoided and a homogeneous, clear, metal resinate, more soluble in hydrocarbon solvents than the metal resinate which has been prepared without the use Of an aldehyde, is formed.

Specific metal resinates which can be prepared by this invention are those of iron, nickel, vana-- dium, copper, titanium, manganese, zinc, cobalt, lead, aluminum, calcium, magnesium, barium, strontium, molybdenum, tin, and others, as described in the examples appearing in this speciflcation. Included are many resinates which have not been prepared prior to this invention. Included also are many metal resinates which although known as such, nevertheless have a higher metal content than has heretofore been possible due to the phenomenon of blocking.

In general the metal resinates may be prepared at temperatures of from 90 C. to 400 C. depending on the type of rosin material used, the specific aldehyde used, and the specific metal compound of a particular metal used. For instance, rosin oil can be reacted with some aldehydes and scQine metal compounds at temperatures as low as 90 C. and some rosins can be reacted with some metal compounds as high as 400 C. Generally, the metal resinates of the metals below hydrogen in the electromotive series can be prepared at temperatures of 90-l20 C. even when rosin is used as the starting material, however the particular rosin material used has to be in a molten state when the aldehyde is reacted. For metals above hydrogen in the electromotive series the preferred range of reaction lies within the range of 120 C. to 320 0., although some resinates containing a relatively high proportion of metal may require slightly higher temperature. some resinates such as those of lead and nickel tend to decompose at the higher temperatures. In such instances we employ 120 C. up to the decomposition point as the preferred range.

The phenomenon of blocking, or setting up into a semi-crystalline mass, for example, characterizes prior manganese resinates. Prior to this invention when manganese resinates of more than 3.5% manganese were desired it was necessary to prepare them by the precipitation method. Such precipitated resins are inferior to refusible resinates in solubility and color. A preferred source of manganese is manganese acetate, but other compounds of manganese, such as the salts of organic acids, particularly the lower members of the fatty acid series and such manganese compounds as manganese dioxide, carbonate. basic carbonate, hydroxide, etc., or various mixtures of suitable compounds may be used. It is to be understood that the products formed with different manganese compounds may be somewhat difierent from those prepared with manganese acetate.

While of an aldehyde is a convenient amount of the aldehyde to use in the preparation of manganese resinates, we are in no way limiting ourselves to this amount, since with high concentrations of manganese, more aldehyde may be desirable, and with small amounts of manganese less is necessary. Clear, homogeneous, petroleum naphtha-soluble manganese resinates containing more than 4% manganese have been prepared from rosin and rosin derivatives and rosin-containing materials which had been reacted with from 0.01% to of an aldehyde.

In general, it is preferred to react the aldehyde with the rosin or rosin derivatives without agitation at temperatures below 170 C. and then to commence the agitation while the temperature is gradually raised to about 230 C. before the manganese is added. However, with manganese resinates containing up to 8.5% manganese prepared using an aldehyde, we prefer to add all the materials together and heat with agitation to about 260 C. before pouring. In this way a product of light color, soluble in petroleum naphtha, can be prepared in a minimum amount of time.

It is usually desirable to react the manganese acetate with the rosin-aldehyde product at temperatures of 250-275 C. and in those resinates which contain 7% to 9% manganese to remove the heat as soon as possible after the desired amount of manganese has been incorporated in the resinate. Since prolonged heating of the rosin-aldehyde-manganese acetate reaction products sometimes causes a partial precipitation of the manganese. This is particularly true of those resinates containing approximately one gram equivalent weight of manganese acetate for each gram equivalent weight of rosin acid.

The reaction of rosin and the aldehyde may be carried out in a closed reaction vessel under pressure, to prevent loss of the aldehyde or the entire reaction with the aldehyde and manganese acetate may be carried out under pressure greater than atmospheric, if desired.

The improved resistance to blocking can be shown since in the presence of from 0.01 to 30% of an aldehyde, a large excess of manganese acetate, above that which will theoretically react with the acid groups present in the rosin or rosin derivative, may be added to the reaction mixture at temperatures of from -400 C. without causing the product 1 block. I

One hundred parts of rosin having an acid value of 168 requires only about 37 parts of manganese acetate tetrahydrate to form the manganese diabietate. However. we have found that 74 parts of manganese acetate tetrahydrate can be reacted with a mixture of 50 parts of methyl rosinate, 50 parts of rosin and 5 parts of paraformaldehyde, to give a clear, homogeneous, petroleum naphtha-soluble resinate.

It was found that the semi-crystalline infusible mass formed by heating a mixture of rosin and manganese acetate could be converted to a resinous state by the addition of an aldehyde to the blocked mass at temperatures in excess of 260 C.

The aldehydes containing from 1 to 5 carbon atoms are usually more effective in making manganese resinates than those of higher molecular weight and since these aldehydes are usually cheaper we prefer to use them. We have also found that mixtures of aldehydes are frequently more effective than any of the pure aldehydes present in the mixture.

The rosin-dihydropyran reaction product forms a manganese resinate of pale color and good solubility characteristics. In this case the dihydropyran ring probably opens to give an aldehyde.

The resinates prepared from formaldehydemodified rosin usually have higher melting points than those resinates prepared from the higher aldehydes. The exact function of the aldehyde in this reaction is not clearly understood, however, a reactive aldehyde group seems to be essential since aldehyde free para-n-butyraldehyde does not affect the blocking tendency of the resinate until a drop of mineral acid is added to the polymer to release the aldehyde.

While the addition of as little as 0.01% of some aldehydes to the rosin brings about a noticeable improvement, as much as 30% aldehyde can be used in the preparation of these resinates, as previously noted. Thus, as much as 35% of manganese acetate may be reacted with a rosin-formaldehyde reaction product, containing 0.01% formaldehyde, without blocking at temperatures of 230-300 C. With larger amounts of an aldehyde more manganese acetate may be added without blocking.

The preparation of aldehyde-modified manganese resinates by this reaction is not limited to acidic derivatives of rosin but take place with such neutral products as rosin oil and rosin esters. In fact we have found it possible to pre-- pare aldehyde-modified manganese resinates of much higher manganese content from a practically neutral rosin derivative such as rosin oil than from ordinary rosin. It is sometimes ad vantageous to use mixtures of these neutral rosin derivatives with rosin to decrease the melting point and increase the manganese concentration of the final product.

Thus, when equal parts of methyl rosinate and rosin are reacted with an aldehyde, as much as 74 parts of manganese acetate maybe reacted with 100 parts of this mixture to give a clear, homogeneous product at reaction temperatures of 220-270 C.

If a product of low melting point is desired, methyl rosinate (the methyl ester of rosin) may be used as the starting material. By reacting 100 parts of methyl rosinate with parts of paraformaldehyde, a product is obtained which will react with 41 parts of manganese acetate at temperatures as low as 100 C. to yield a clear, homogeneous, manganese resinate which is soluble in petroleum naphtha. This product is a viscous liquid at room temperature.

Similarly, when rosin oil or tall 011 is reacted with an aldehyde, the resulting product may be reacted with manganese acetate to give a clear, homogeneous, petroleum naphtha-soluble manganese resinate which is a viscous liquid at room temperature.

Since manganese resinates usually have rather high melting points we have found it advantageous to add small amounts of liquid rosin derivatives such as rosin oil, methyl abietate, etc. Thus, when 100 parts of rosin were reacted with 5 parts of formaldehyde, and to the reaction product was added 1 part of rosin oil and this mixture was then reacted with 45 parts of manganese acetate, a clear, homogeneous manganese resinate was produced which had a lower melting point, and increased solubility, compared with a manganese resinate made in the absence of the rosin oil.

In referring to manganese resinates having a high manganese content, we do not mean to limit ourselves to acid or even neutral manganese resinates, but also to include products containing more manganese than that required to react completely with the carboxyl groups present.

When we refer to the properties of these manganese resinates, we refer to the property of the materials as a whole. This is done to avoid controversy over whether the manganese resinate itself or the concomitant impurities are responsible for the observed properties.

Zinc resinates according to this invention, may be made either by fusion reaction (1. e. a

reaction carried out under conditions such that one or more of the reactants is in a fused state) or by reaction in solvent media.

In the reaction of rosin with zinc compounds to form zinc resinates by prior methods, the re action apparently proceeds with the formation of a zinc abietate or in some cases to form a mixed salt, such as zinc acetate-abietate. In either' case the zinc content obtainable appears to be limited by the number of carboxyl groups available. However, we have discovered that such rosin derivatives as methyl abletate, ester gum, decarboxylated rosin, or rosin oil, having acid numbers less than 20, after being reacted with an aldehyde will react with a suitable zinc salt, such as 21110 acetate, to yield a clear, homogeneous and permanently reluslble zinc resinate completely soluble in the ordinary varnish solvents. Liquid decarboxylated rosin with an acid number OI 20, when reactedwith 5% of para- -formaldehyde, gave a product that would react with an equal weight zinc acetate to form a zinc resinate or n grace with a melting point of 129" C. (ball and ring). since such zinc compounds contain more znlc than can be accounted for by the reaction or the carboxyl groups with zinc L0 form either the zinc oiabietate or the mixed a'bietate-acetate, the reaction must proceed by a different mechanism than it does in the case of the rosin-zinc compounds prepared in the absence of an aldehyde.

While zinc oxide is a convenient compound to use in the preparation of zinc resinates, other forms of zinc, such as Ilnely ulvlueu zinc metal or zinc salts, which will react with the rosin, such as zinc acetate or formate may be used. It is to be understood that in some cases the products formed with different zinc salts will be somewhat different from those prepared with zinc oxide.

If an acid zinc resinate is desired, we prefer to start with a rosin which has been reacted with less than 5% of aldehyde, such as formaldehyde and, in general, for resinates containing between 5% and 8.5% of zinc, we prefer to use less than 1% of formaldehyde.

In general, it is also preferred to react the aldehyde with the rosin without agitation at temperatures below about C. particularly those resins in which less than 1% of aldehyde is to be added, and then to commence the agitation while the temperature is gradually raised to about 230 C. before the zinc is added.

Thus, with 5% of formaldehyde, 14.0% of zinc oxide may be added and with 0.1% formaldehyde, 8.4% of zinc oxide may be added.

Also, it was found by using 8% of formaldehyde, up to as much as 12 parts of zinc oxide could be added and all of the ingredients mixed together and heated to about 250 C. without blocking to form a permanently refusible resin. However, we prefer to react the rosin with about 5% of formaldehyde first by heating the mixture of rosin and formaldehyde up to 150 C. without agitation and adding additional formaldehyde as desired with agitation. In this manner is was found that considerable quantities of formaldehyde could be reacted with rosin without undue loss of the vapors of formaldehyde. We prefer to add zinc oxide slowly to this reaction product at temperatures in excess of 230 C. with agitation.

However, when higher concentrations of formaldehyde are desired, the reaction of rosin and formaldehyde may be carried out in a closed reaction vessel under pressure to prevent loss of 11 the formaldehyde, or the entire reaction with formaldehyde and the zinc compound may be carried out under pressure greater than atmospheric, if desired.

If an organic acid is used to catalyze this reaction, we prefer to place all constituents together in a petroleum solvent; however, these preferences are to be in no way limiting upon our method or product as will be shown herein below.

The improved resistance to blocking can be shown, since in the presence of about 8% or more of formaldehyde, a large excess of zinc oxide above that which will theoretically react with the acid groups'present may be added to the reaction mixture at 250 C. without causing the product to block. The excess zinc oxide remains in suspension in the product with no apparent harmful effects.

It was also found that the semi-crystalline infusible mass formed by heating a mixture of rosin and zinc oxide could be converted to a resinous state by the addition of formaldehyde to the blocked mass at about 250 0.

While the products prepared by the methods described here are in some-respects similar to the commercial zinc resinates, there is considerable difierence in some physical and chemical properties. These compoundsprepared with an aldehyde show much greater solubility in the low solvency hydrocarbons than is shown by zinc resinates of comparable zinc content prepared from rosin or mixtures of rosin and polymerized rosin. The'viscosities of the solutions of zinc-rosin-aldehyde reaction products are usually lower than the viscosities of comparable products prepared without an aldehyde.

In general, as the amounts of formaldehyde and zinc used are increased the melting point of the product increases and the color of the product becomes darker. The color is also darker with some aldehyde derivatives than others, for example, the hexamethylenetetramine zinc resinate gave products darker than D grade rosin,

whereas, the products formed with aqueous formalin solutions were only slightly darker than than the original rosin.

The properties of zinc resinates made from aldehydes other than formaldehyde will be apparent from the specific data presented in this specification.

Of particular interest are resinates in which calcium is substituted fora portion of the zinc. These mixed calcium-zinc resinates have higher melting points than the corresponding zinc resinates prepared from aldehyde-modified 'rosin. These mixed resinates are prepared simply by substituting equivalent amounts of calcium compounds, for example calcium hydroxide, for the zinc compound in a zinc resinate preparation as described in the foregoing paragraphs. calcium-zinc resinates are of particular importanc'e wherein the calcium to zinc ratios are These 12 a cobalt compound is reacted with rosin in the presence of an aldehyde, its normal tendency to block is avoided, and a permanently refusible, homogeneous product is formed.

One hundred parts of a rosin having an'acid value of 168 requires only about 38, parts of cobalt acetate tetrahydrate to form the cobalt diabietate. When the rosin has been previously reacted with about 2 to 4% of an aldehyde, 100 10' parts of cobalt acetate can be reacted with v100 parts of this rosin-aldehyde product. with as little as 0.01% of an aldehyde, 41 parts of cobalt acetate tetrahydrate can be reacted with 100 parts of rosin. Also, with of formaldehyde, as much as 350 parts of cobalt acetate tetrahydrate can be reacted with 100 parts of rosin without blocking, although, at such high cobalt concentrations a noticeable precipitate is formed during the reaction.

In general, as the amount of an aldehyde used is increased, the solubility of the corresponding cobalt resinate increases and the time for the reaction to go to completion decreases. It is easy to follow the course of the reaction, since as the cobalt acetate reacts, the color of the reaction mixture usually changes from a purple to a deep blue.

When a soluble cobalt resinate of very high metal'content is desired, the more soluble, deep blue .cobalt resinate can be prepared by reacting cobalt acetate with the rosin-aldehyde product until the color changes from blue to purple.

More aldehyde will change the color to blue again and then more cobalt acetate can be reacted. This procedure may be repeated until the desired cobalt content is reached.

Nickel resinates are somewhat more difllcult.

to prepare than the corresponding cobalt resinates. The nickel resinates have melting points similar to those of zinc, but are-clear green in color. Nickel resinates tend to decompose at comparatively low temperatures, 1. e. 265-270" C.

Aluminum resinates differ inseveral respects from all other resinates prepared. They have unusually high melting points and they seem to be characterized by very high temperatures of reaction and decomposition. Aluminum resinates generally have melting points in excess of 220 C., and do not decompose when heated at 370 C.

All aluminum resinates seem to have a high solubility, i. e. from 10 to 50% in petroleum naphtha, also soluble in varsol and turpentine. They all have a very fast rate of solution, 1. e. they dissolve in from 5 minutes to several hours. However, the aluminum resinates generally set into a gel on standing after being dissolved in solvent. These gels are unique in/that the whole of the material is gelled, that is, solvent also, and the gels are very stable. Even shaking them on a shaking machine only causes the material to break temporarily, and upon again, standing a short while, no change is apparent in the prior processes, it has heretofore been necessary 3 to use such constituents as partially polymerized or heat treated rosin to obtain a cobalt resinate containing more than 4% cobalt. When These'resinates may find uses in such materials as greases and lubricants where a gel is understood that they are not to be considered as limiting. For instance, the metal contents of the resinates prepared, in many cases, are maxima or are greater than found in the resinates of present day commerce. In every instance resinates may be made of lower metal 14 raised to 230 C. A cerium compound, prepared by dissolving 20 parts of cerium oxalate in nitric acid, precipitating with sodium hydroxide, and after washing and drying, dissolving the material content than illustrated, by the method of our in acetic acid and adding this solution to the hot invention. rosin. The temperature was raised to 270 C. and

EXAMPLES 5 after 3 hours had not cleared. The reaction prodnot had a heavy white precipitate present and One hundred parts of WW gum rosin were was opaque. heated to about 130 0. without agitation. Agitation was commenced and the temperature was EXAMPLES 17.45 raised as indicated in the following table. At this temperature, the metal compounds listed below One hundred parts of WW gum rosin were were added in the amounts as indicated. The heated with an aldehyde as listed in the table metal resinates prepared in this manner without below to about 130 C. without agitation. Agithe use of an aldehyde exhibited the properties tation was commenced and the metal compound and characteristics shown in Table 1. in the amounts and types as indicated in the table Table 1 METAL RESINAIES WITHOUT AN ALDEHYDE Example number 1 2 3 l 4 1 5 6 Rosin, parts by weight 100 100 100 100 100. Metail rlzlotmpounds, parts by 22. 6.

weg Metal compounds N 2101133020.. Zr(O:Ha0:)4... Mn(C;H=Oi)r4H1O. Reaction time, hours 3 2 3 3 2. Maximum reaction tem- 275 280 310.

perature, C. Reaction product pphfigt in OPAQ Black 0PAQ... Black OPAQm. Blocked.

nap a. soluhhitllllty in petroleum incompletely Heavy ppt. Heavy ppt Heavy black ppt. Heavy black ppt. ppt.lncompletely sol.

nap a. so

Example number 7 8 9 10 11 Rosin, parts by weight. 100 100 100 Metal comhpounds, parts 30 6.5.

y weig t. Metal compounds N i(C2Ha0z)r4HzO. Cu(C2H:Oz)rHzO.. Zn(C,H 0 -2H:O. Reaction time, hours.... 3 3 3 2. Maximum reaction tem- 130 300.

perature, C. Reaction product OPAQ OPAQ. Grecn Blocked. Solubility in petroleum completely ppt Heavy green ppt Heavy ppt.

naphtha.

Example number l2 l3 14 I 15 Rosin, parts by weight 100. Metal compounds, parts by weight 15. Metal compounds SD20: Reaction time, hours Maximum reaction temperature, 220. Reaction product Gray glazed. Solubility in petroleum naphtha Heavy gray ppt.

1 The metal compounds used in Examples 4, 5, and 15 were slurried in acetic acid and added as a slurry to the hot rosin.

EXAMPLE 16 One hundred parts of WW gum rosin were heated to about 130 C. without agitation. Agitation was commenced and the temperature was following were added slowly as the temperature was gradually brought to that indicated in the table. After the reaction time as listed, the products had the characteristics shown in Table 2.

Table 2 METAL RESINATES PREPARED FROM ALDEHYDE-MODIFIED ROSIN Example number 17 Rosin, parts by weight Aldehyde, parts by weight.

Metal compounds, parts by weight Metal compounds... Reaction time, hours Maximum reaction tempera Color grade Melting point, ring and ball, C Time in hours to dissolve 20% solids in petroleum naphtha (B. P. 95115 0.).

S0]. in HzO..

z00. l araiormaldchyde.

l Melting point sample shattered on cooling.

Table 2-Continued METAL RESINATES PREPARED FROM ALDEHYDE-MODIFIED ROSIN-Continued Example number 22 Rlndsig, sorts by igeightufi 00 A e e or s wei 1 y p y g Acctaldehyde Aldehyde Metal compounds, parts by weight. Metal compounds Reaction time, hours Maximum reaction temperature, C Color grade Melting point, ring and ball, C. Time in hours to dissolve 20% solids in etroleum naphtha (B. P. 95- 115 0.).

Paratorm aldehyde. l5 F500:

J1500 roe-deride:

100 i dir'd'rbhih'iiira'fjj 82 g :H:O2)2-4 z0 200. Phraldehyde.

Example number 23 100 5 Paraiormuldehyde.

Rosin, parts by weight. Aldehyde, parts by weight. Aldehyde Metal compounds, parts by weight.

Metal compounds Reaction time, hours Maximum reaction tempcrature, C.

Melting point, ring and 127 Time in hours to dissolve 20% solids in petroleum naphtha (B. P. 95- 115 0.).

Example number 31... gLKCI ZODTHIO Flake Paraformaldehyde.

ZnO.

Rosin, parts by weight Aldehyde, parts by weight.. Aldehyde Metal compounds, parts by weight Metal compounds Reaction time, hours 6. Maximum reaction temperature, "C Color grade I Melting point, ring and ball. "0 Time in hours to dissolve solids in petroleum naphtha (B. P. 95-115 0.).

Example number arai'ormaldehyde. l bCOrPb(OH)z. 250.

Rosin, parts by weight. Aldehyde, partsbyweight. 5 Aldehyde 5 Paraiurmaldehyde.

2PbCO;-P b(OH)1. Lionnomno 4 3 Maximum reaction perature, 0

Color grade...

Melting point,

ball, 0.

Time in hours to dissolve 20% solids in petroleum naphtha (B. P. 95- 115 0.).

Soluble in H2O Soluble in H20.

Paralormaldehyde 100. %araiormaldehyde.

33 .3 z a02)r 290.

Example number -L 41 42 Rosin, parts by weight 100 100 100 Aldehyde, parts by weiglit Aldehyde Metal compounds, parts by weight. 42.5 32.8 36.4 g UI( 2 l 2)212Ll2O 2Cd(C2HaO2)z2Hr0 Metal compounds Ba(CQH;O)1H;O

Reaction time, hours l Maximum reaction temperature, 250

Color grade .N Melting point, ring and ball, C 125.. Time lIl. hours to dissolve 20% )6 solids in petroleum naphtha (B. P. 95-115 0.).

5 Paraformaldehyde. l

5 Paraiormaldehyde.

Paraiormald hyde.

Melting point sample shattered on cooling,

EXAMPLES 46-56 One hundred parts of. WW gum rosin and 5 parts of an aldehyde were heated to about 170 C. without agitation. Agitation was commenced Metal compounds in the amounts and types indicated were slurried with parts of acetic acid and the slurry added slowly to the reaction mixture as the temperature was raised slowly to that and the temperature raised to about 220 C. indicated in Table 3. After the reaction times 18 ball, and took several hours to dissolve in petroleum naphtha. This solution gelled on standing.

1? indicated, the products had the characteristics shown in Table 3.

Table 3 METAL RESINATES PREPARED FROM ALDEHYDE-MODIFIED ROBIN Example number 46 47 48 49 Rosin, parts by weight 100 100. Aldehyde, parts by weight. 5. Aldehyde Paratormaldehyde. n-hept-aldehyde. Metal compounds, parts by weig 6 6. Metal compounds M001. Reaction time, hours 3 6. Maximum reaction temperature, C. 275. Color grade Green. Melting point, ring and ball, 0.- 92. Time in hours to dissolve 20% solids l.

in petroleum naphtha (B. P. 95-

Example number 50 51 52 53 Rosin, parts by weight 100 100 100 100. Aldehyde, parts by weight- 5 5 5 6. Aldehyde Paraformaldehyde. Paraiormaldehyde. Paraldohyde Paraiormaldehyde. Metal compounds, parts by weight... 14.4. Metal compounds BuOrCOi-HrO Cr(OH) (00;). Reaction time, hours 3 4 3. Maximum reaction temperature, C. 270. Color Grade"... Clear Green. Melting point, ring and ball. C. 99. Time in hours to dissolve 20% solids M.

in petroleum naphtha (B. P. 95-

Example number 54 65 56 Rosin, parts by weight 100 100. Aldehyde, parts by weight. 5 6 5. Aldehyde Paraiormaldehyde. Pami'ormaldehyde. Metal compounds, parts by weigh (i l5. Metal compounds l l- Reaction time, hours i 4 2. Maximum reaction temperature, C Color grade G M- Melting point. ring and ball. C 81. Time in hours to dissolve 20% solids in petroleum naphtha 9.; 56.

EXAMPLE 57 EXAIVIPLE 59 One hundred parts of WW gum rosin and 5 parts of paraformaldehyde were heated to about 170 C. without agitation. The agitation was commenced and the temperature was increased to 230 C. A cerium compound was prepared by dissolving 36 parts of cerium oxalate in nitric acid, precipitating with sodium hydroxide and after washing and drying the precipitate, dissolving it in acetic acid. This acetic acid solution containing the cerium compound was added slowly to the hot rosin. After 3 hours, the prodnot had a color grade of B, melting point 104 O. ring and ball, and took 20 minutes to dissolve 20% solids in petroleum naphtha.

EXAMPLE 58 One hundred parts of WW gum rosin and. 5 parts of paraldehyde and 5 parts of butyraldehyde were heated to about 170 C. without agitation. Agitation was commenced and the temperature raised to 230 C. A cerium compound was prepared by dissolving 36 parts of cerous sulfate (C2(SO4) 3181120) in water, precipitating with sodium carbonate and after washing and drying the precipitate, dissolving it in acetic acid. This acetic acid solution containing the cerium compound was added slowly to the rosin-aldehyde product as the temperature was raised slowly to 260 C. After 6 hours, the product had a color grade of H, a melting point of 141 C. ring and One hundred parts of WW gum rosin and 5 170 C. without agitation. Agitation was commenced and the temperature was raised to 230 C. A titanium compound was prepared by dissolving 10 parts of titanium dioxide (TiOa) in sulphuric acid and precipitating with sodium carbonate. After washing with water and drying, the titanium compound was slurried in acetic acid. This slurry was added to the hot resin as the temperature was gradually increased to 300 C. After 4 hours, the product had a color grade of G, melting point 83 O. ring and ball, and took 30 minutes to dissolve 20% solids in petroleum naphtha. (boiling point -115" 0.). A light. white material precipitated on standing.

EXAMPLE 60 ne hundred parts of WW gum rosin and 5 pa .s of paraldehyde were heated to about 170" C. without agitation. Agitation was commencedand the temperature was raised to 230 C. A titanium compound, prepared by adding parts of acetic acid to 26.5 parts of titanium tetrachloride, was added to the hot resin slowly as the temperature was raised to 260 C. Alter -6 hours, the product had a color grade of B,

19 EXAMPLE 61 resin as the temperature was raised to 250 C.

After 3 hours, at 250 C. the product had a color grade of G, a melting point of 104 C. ring and ball, and took 30 minutes to dissolve 20% solids in petroleum naphtha.

EXAMPLE 62 One hundred parts of WW gum rosin and 5 parts of paraformaldehyde were heated to about 170 C. without agitation. Agitation was commenced and the temperature was raised to about 250 C. A lanthanum compound was prepared by dissolving 10 parts of lanthanum nitrate in water, precipitating with an excess of sodium carbonate, filtering, washing, and slurrying this precipitate with acetic acid. This slurry was added while the temperature was raised slowly to 250 C. After 3 hours, the product had a ring and ball melting point 01' 81 C. and took 20 minutes to dissolve 20% solids in petroleum naphtha. Color grade E.

EXAMPLE 63 One hundred parts of WW gum rosin and 5 parts of paraformaldehyde were heated to about 170 C. without agitation. Agitation was commenced and the temperature was raised to 230 C. Fifteen parts of zirconium acetate, dissolved in water were added slowly as the temperature was raised to 280 C. After 3 hours, the product had a color grade of F and a melting point of 128 C. ring and ball, and took /2 hour to dissolve 20% solids in petroleum naphtha.

EXAMPLE 64 One hundred parts of WW gum rosin and 5 without agitation. Agitation was commenced and the temperature raised to 250 C. A solution was prepared by dissolving 4 parts of beryllium oxide in sulphuric acid and precipitating it out with sodium hydroxide. After filtering the precipitate it was dissolved in acetic acid. The acetic acid solution of the beryllium compound was added slowly while the temperature was raised to 310 C. After 3 hours, the product had a color grade of G, melting point 128 O. ring and ball, and took 1 hour to dissolve 20% solids in petroleum naphtha.

EXAMPLES -66 One hundred parts of WW gum rosin and 5 parts of paraformaldehyde were heated to about 130 C. without agitation. Agitation was commenced and the rosin-formaldehyde product allowed to cool to the desired temperature. Metal compounds in the amounts and types indicated were added slowly. After the reaction times indicated, the products had the characteristics shown in Table 4.

' EXALIPLES 67-87 One hundred parts or its equivalent of the type rosin as indicated in Table 5 were reacted with an aldehyde to about 170 C. without agitation. Agitation was commenced and the temperature was increased to about 230 C. Metal compounds were reacted in the amounts and types indicated, as the temperature was increased to that listed in the table following. The products had the parts of paraiormaldehyde were heated to 170 C. 45 characteristics shown in Table 5.

Table 5 v METAL REBINA'IES FROM vsmous ROBIN MATERIALS Example number as Rosin,

r0 Lldebydes, parts by weight.. 4 iildehydes Metal compounds, parts by 35 weight. Metal compounds ion time, hours Maximum reaction temperture "C by weight sin folymerizod" l Color grade 4 Paraiormaldehyde 35 35 100. 4Rosin acids. garaformaldehyde.

gPbCOt-PlKOHh. 250.

fleging point, ring and ball,

Tar; inlaiiurisn to dissolve e0 8 DO TO eurn naphtha (B. P. 95-115 0.).

Example number Rodn, parts by Weight to in etel compounds, parts by weight. Metal compounds .Reectlon time, hours Maximum reaction temperature, "0 Color grade Melting point, ring and ball, C Time in hours to dissolve 20% solids in petroleum naphtha (B. P. 951l5 0.).

ZnO 6 10o. glosin acids. garaformaldehyde.

ZnO ZnO. 5 3. v

100 Stabilized 5 Earaiormaldehyde, z'fifiIIIIIIIIIIIIII over I The stabilized rosin used in Examples 70, 74, 78, 79, and 84 was a disproportiomted rosin prepared by U. 8. Patent 2.239.555.

The duhee indicate thin characteristic was not measured.

Table Contlnued Example number 30 ype rosin Po er zed. Aldehydes, parts by weight 5. m Aldehydes i i v i Paraiormaldehyde. Metal compounds, parts by \VllgllL 41. Metal compounds Co(C:H1O:)1-4H;O. Reaction time. hours Maximum reaction temperature, "C 280. Color grade Blue. Melting point, ring and ball, "C 11 142. Time in hours to dissolve 20% solids in 5.

petroleum naphtha (B. P. 95-115" 0.).

Example number 81 32 33 34 Rosimparts by weight o 100 100. T e rosin Resin acids Stabilized; A dehyde, parts by weight. 5 5. Aldehydes i. Paraiormaldehyde.... Paraformaldebyde.

Metal compounds, parts by weight. Metal compounds Reaction time, hours Maximum reaction temperature, Color grade Melting point, ring and bull, C Time in hours to dissolve solid n petroleum naphtha (B. P. 95-ll5 0.).

Example number 86 87 Rosin, parts by weight 125 l 100.

T pe rosin Oleoresrn. Resin acids Hydrogenated.

A dehydc, parts by weight Aldehydes Paralormaldehyde.

Metal compounds, parts by wcigbt Metal compounds Reaction time, hours Maximum reaction temperature Color grade Melting point, ring and bell, C

Time in hours to dissolve 20% solids in petroleum naphtha (B. P

g wz aor) 24 10 2 50.

over 200.

1 The stabilized rosin used in Examples 70, 74, 78, 79, and 84 was a disproportionated rosin prepared by U. 5. Patent 2,239,655.

EXAMPLES 88-1 1 1 One hundred parts of WW gum rosin and temperature was raised to about 230 C. Zinc oxide was added slowly as the temperature was aldehydes in the amounts and types as listed in 45 raised as indicated in Table 6. When 10 parts Table 6 were heated to about 170 C. without of zinc oxide had reacted, the resinates hadthe agitation. Agitation was commenced and the characteristics shown in Table 6.

Table 6 METAL RESINATES PREPARED USING ALDEHYDES Example number 88 89 90 91 93 Rosin, parts by weight 100 100 100 100 100 v100. Aldehydcs, parts by weight l 5 l 1 5 5. Aldehydes Pnraldehyde. Aoetaldehyde. Benzaldebyde. Dillydropyranu Propioneldehyde n heptaldebyde. Zinc oxide, parts by weight l0 l0 10 10 10 10. Reaction time, hours u l 6 Maximum reaction temperature, C 275 260, Melting point, ring and ball, "0 121 105. Color grade N M Time in hours to dissolve 20% solids in )6 petroleum naphtha (B. P. -115 Example number 94 95 96 97 98 Rosin, parts by weight 100 100 100 i. 100 100. Aldehydes, parts by weight" 5 i. 1 5 6 5. Aldehydes i B l1 11 t r a l d c Salicylaldebyde. C {1 mm a l d e 2-ethyl-hexaldehyde. Anisaldebyde.

Y y e. V Zinc oxide, parts by Weight 10 10 10. Reaction time, hours 6 i. 6 6. Maximum reaction tcmpcmture, C 260 255 Melting point, ring and bull, C 128 153 l12. Color grade H E G. Time in hours to dissolve 20% solids in petroleum l 1 l.

naphtha (B. P. 95-115 (3.).

I This aldehyde prepared according to Delaly, Bull. Soc. Chim. 53, 301-321 (1983).

EXALIPLES 112-137 Table '7 were heated to about 170 0. without Table 6-Continued 1 METAL RESINATES PREPARED USING ALDEHYDES --Continued Example number 99 100 101 102 103 y 104 Rosin, parts by wnivhl: 100 100 100 100 100 100. Aldehydes, parts by weivht Ii 1 I l 0. 1 i. Amenydes echlorobenl-aldehydm FuriuraL- Crotoneldehyde. lsgbrtyralde- Glyoxal Piperonal,

y e. Zinc oxide, parts by weight. 10. Reaction time, hours 3 6. Maximum reaction temperature, "C 275. Melting point, ring and ball, C 120, Color grade B Time in hours to dissolve solids in petroleum naphtha (B. P. -115" 0.).

Example number 105 106 107 108 109 110 111 Rosin, parts by Weig 100 100 [00 mo 100 100 100. Aldehyde, parts by weight 1 1 l-.- 1 5 5 6. Aldehydes Glucose... Acroleim. c-Nitrobenmldehyde-- ChloraL. Aeetal. MethylaL. Stgari l A de. Zinc oxide, parts by weight 10.. 10. y Reaction time, hours. 6 5. Maximum reaction tempera 260 275. Melting point, ring and ball, 121 94 Color grade B H B K. Time in hours to dissolve 20% solids 5 K 3 )4 in petroleum naphtha (B. P. 95- 0.).

temperature was increased to about 230 C, Metal compounds in the amounts and types in- One hundred parts ofwwgumrosin and alde- 3o dicated were added and the temperature was hydes, in the amounts and types indicated in raised to that as listed in the table below.

the times listed the metal resinates had the char- 'lrionnohthotndeumoiubnl ont'lhmmethylme.

agitation. Agitation was commenced and the acteristics shown in Table 7.

Table 7 METAL REBINATES PREPARED FROM MIXED ALDEHYDE-MODIFIED ROBIN Example number 112 113 114 115 11s Rosin, parts by weight 100... 100 100 100 100, Aldehydes, parts by weig 2-" f" g Aldehydes Paraldeh do: P'r'ldeh dor'r'meh de Paraldehydefaraldahyda,

Benzalde yde. Aoetalde yde. o-Ohloronzaldehyde. Butyraldehyde" Paraio'rmaldehyde. Metal compounds. parts by weight. l0. l0. l0 10 10. Metal compounds ZnO ZnO. Reaction time. hours. e Maximum reaction to 275. Color grade H. Meltin point, ring and ball, C. I 116. Time n hours to dissolve 20% solids in )6. M... M,

petroleum naphtha (B. P. 95-ll5 0.).

Example umber 117 118 119 120 Rosin, parts by weig 100 100 100 100. Aldehydes, parts by weightv f 2 Aldehydes Benzaldeh do P at aiormaldebydmr: fir'fdfi'fijjiiii lqueous formaldehyde,

Paraiorm dehyde. o-Chloro-benmldehyde Propiona dehyde. Paraldehyde. Metal compounds, parts by weight"-.. l0. Metal compounds ZnO ZnO ZnO Reaction time. hours. 6 B 6.

Maximum reaction temperature, C- 275 260 260. Color grade M F F. Melting oint, ri Ind ball, C 108 117 125. Time in ours to lve 20% solids in petroleum )6 l6 naphtha (B. P. 95415" 0.).

Example number 121 122 123 124 125 Rosin, parts by weight. 100 100. 100 100 100. Aldehydes, parts by weight g g g g Aldehydes' A queous formaldehyde 'lrioxane Trioxane Paraldeh d e l araldehyde.

Be'nzaldehyde Paraldehyde.. Benzaldehyde- Benzalde yde Propionaldehyde. Metal compounds,partsby weight. 10. 10. 1 34.6... 34.6. Metal 00m unds ZnO ZnO ZnO Zn(C,H;0|)|-2H1O. Zn(C:BsO:)1-2H|O. Reaction t me, hours. 0 6. 6. 6 6. Maxmum reaction temperature, 260 27 27 21 275. Color a. M M E. K. Melting point, ring and ball, 0... 1 101 110. Time in hours to dissolve 20% 1 36-m- K. $6.

solids in etroleum naphtha (B.

troleum naphtha (B. P. 95-115 0.).

l Trioxsne is the trade name for Du Ponts trioxymethylene.

EXAMPLES 138-144 One hundred parts of WW gum rosin, aldehydes in the amounts and types indicated, and metal compounds as listed were heated to 230 Table 7-Continued METAL RESINATES PREPARED FROM MIXED ALDEHYDE-MODIFIED ROBIN-Continued Example number...- 126 127 128 129 Rosin, parts by weight 100 100 100.- Aldehydcs, parts by weight g g Aldehydes r'idfi'filrdaau'ra'rnuaaitaai 'l rioxane Propion dehyde. Paraldehyde Benzsldehyde. Metal compounds, parts by weight i 1 10 i Metal compounds. Zfigbfiiiiifiiifffi. zigciutoetzmo.

1 Zn Zn Reaction time, hours 3 Maximum reaction temperature, 275. 275. Color gr M M. Melting int, rinfiiauni bell, 0 106. Time in ours to lve 20% solids in petroleum naphtha (B. 1?. 95-115 0.).

Example number 130 131 132 13s Rosin, partsbyw 1m 1m 100. Aldehydes, parts by weight R Aldehydes. Pal-aldehyde Reraldehyde. Trioxene.

Butyraldehyde Paraldehyde. Metal oompoimds, parts by weight L2 1 (11.2.

eI Metal compounds Zn metal Zn metal.

ZngCulhOzh 2H10 CESCgHaOflrHgO. Zn Zn Reaction time, rs 6 5. Maximum reaction temperature, C 27 275. Color grade- K. W G. Melting int, ring and bell. C 102 109. Time in ours to dissolve solids in pe- A )4.

troleum naphtha (B. P. -115 0.).

Example number 134 135 136 137 Rosin, parts by w ht 100..- 100. Aldebydes, parts by weigh g g g Aldehydes Raraldehyde Raraldehyde Trioxene 1 Rel-aldehyde, Buty l- Butyraldehyde Butyraldehyde Paraldebyde dehyde. Metal compounds, parts by'weig 1 1 0.2-.-. II 9:

Metal compounds 0'8 chimp-m0.--" zn c,H,o, ,-2H,o,

a Ca 0H Zn Zn Reaction time. hours 4. 4. Maximum reaction temperature, C 27 276. Color grade- N. N. Melting oint, ring and ball, C 149-.. 132. Time in ours to dissolve 20% solids in pe- 1..... 54.

C. without agitation. Agitation was commenced and the temperature raised to 275 C. After from 2 to 6 hours, the products had the char:- teristics listed in Table 8.

) Table 8 MIXED METAL RESINATES PREPARED FROM ALDEHYDE-MODIFIED ROBIN Example number 138 139 140 141 Rosin, parts by weight 100 100 100. Aldehydes, parts by weightg 5 5. Aldebydes Trioxene 1 Pal-aldehyde Paraldehyde.

, Paraldehyde Metal compounds, parts by weight... 0. 2 1. 1. 9. Metal compounds Zn metal "ziigoliijolii z'fifdl 8 s. ZnO.

Reaction time, hours i. Maximum reaction temperature, C. 275. Color grade.- N. Melting int, r and ball, C 119. Time in ours to lve 20% solids in 34 petxolemnnaphtha (B. P. lid- 0.).

1 Trloxane in the trade name for Du Pont'l trioxymethylene.

" Table 8-Continued MIXED METAL REBINATEB PREPARED FROM ALDEEYDEMODIFIED ROBIN-Continued Example number 142 143 s 144 Begin, parts by weight 100 100 100. Aldehydu, parts by weig 2 g g.

d Paraldehyde Peraldeh de in h my Butyraldehyde 'Irioxane rwydz Metal compounds, parts by weig 1 i o 9: I 9:

Metal compounds CifiaOflrHiO Co OH); Ca 0151),. I

- Ca 0H Cu CgHaOih-HgO Ca 0111;091:18 0.

Reaction tim hours 4 a 5.

Maximum reaction temperature, C 275 275 m a Color gr I K I.

Melting Eoint, r and ball C 119 117 137.

Tug- :1 n m lve20%aolidsinpetroleum naphtha (B. P. 1 1 1;;

l Trioxane is the trade name (or DlfPont'e trioxymethylene.

1 Refluxed the mixture, a trap was inserted and volatile material removed to a maximum temperature 01200' O.

EXAMPLE 145 One hundred parts of ww gum rosin, 5 parts of paraldehyde, 9 parts of zinc oxide, 1 part 01! calcium hydroxide, and 1 part of calcium acetate were refluxed without agitation for 5 hours. (Reflux temperature controlled at 200 C.) A

trap was inserted and the volatile matter removed petroleum naphtha (B. P. 95-115 c.)

EXAMPLE 146 One hundred parts of WW gum rosin and 0.03

part of paraldehyde were heated to about 170 C.

without agitation. Agitation was commenced and the temperature was increased to 275 C. Ten parts of zinc oxide were added slowly. After 4 hours, the metal resinate had a color grade of M, a melting point of 116 C. ring and ball, and

took 30 minutes to dissolve 20% solids in petro leum naphtha (B. P. 95-115 C). 1

EXAMPLE 147 One hundred parts of WW gum rosin and 30 parts of 2-ethyl-hexaldehyde were heated to reflux (about 200 C.). Zinc oxide was added until 10 parts were present in the mixture. Reflux was continued for 5 hours. A trap was inserted and the volatile material removed to a maximum temperature of 275 C. The metal resinate prepared in this manner had a color grade'ot H, a melting point of C. ring and ball, and took 45 minutes to dissolve 20% solids in petroleum naphtha (B. P. 95-115 C.)

EXAMPLE 148 One hundred parts 0! WW gum rosin and 10 parts of paraldehyde were heated to 170 C. without agitation. Agitation was commenced and the temperature was raised to 230 C. Ten parts of zinc oxide were added as the temperature was raised to 275 C. At this temperature 1 part more (total 11 parts) of zinc oxide was added. At' 5 hours, the metal resinate had a color grade of M, melting point of 108 O. ring and ball. and took 30 minutes to dissolve 20% solids in petroleum naphtha (B. P. 95-115" C.). Further addition of zinc oxide whitened the resinate, but no blocking occurred.

EXAMPLES 148-178 One hundred parts 01' the rosin derivatives as listed in Table- 9 and aldehydes in the amounts and types indicated were heated to about 170 C. without agitation. Agitation was commenced and the temperature raised to 230 C. Metal compounds in the amounts and types listed below I were added as the temperature was raised to that indicated. After from 4 to 6 hours the products had the characteristics shown in Table 9.

Table 9 METAL REBINATES PREPARED FROM ROSIN DERIVATIVES Example number 150 161 152 Rosin derivatives, parts by w ivh 100 100.

Rosin derivatives Methyl abietate Tall oil. Aldehydes, parts by weight 5 5 5 5. Aldehydes Paraldehyde. Butyraldehyde Benzaldehyde n-Heptaldehyde. Metal compounds, parts by weight" 79.6 54.6 54.6. 1

Metal com S Zn(C1H|O1)|-2H1O. ZI1(C|H;O1) 2-2H2 Z11(CIHI02) I'2HIO Zn(.C1H;0,);-2H 0. Reaction t me, hours" R 6 5 5.

Maximum reaction temperature, C

r grade hours to dissolve m solids in petroleum naphtha (B. P. 96-116 0.).

Soft rosin. 136.

example above had an acid number oi. 7.

Table 9-Cbntinued METAL RESINATES PREPARED mom ROBIN DERIVATIVES-Continued Example number 153 154 155 156 50. Rosin derivatives, parts by weight 1m 1m 50' Rosin derivatives Methyl Abietate Tall oil Eater gum Rosin and Methyl abletate. Aldehydes, parts by weight. l 0.5- 2. 5. Aldehydes Paraldebyde Benzaldehyde Butyraldehyde Paraldehyde. Metal compounds, parts by weight. 82 41. Metal 001111301111 8 C(CrH;Os):-4Ha C0(CaHiO:)2-4Hs0...- C0(C:Hi0|):-4H10--- Ml1(CzH;Oz)z-4H;O. Reaction time, hours 6 6 6 6. Maximum reaction temperature, 0. 250. Color grade E. Meltinilpoint, ring and ball, C 158. Time hours to dissolve 20% solids in 7.

petroleum naphtha (B. P. 95-1l5 0.).

Example number 157 158 159 160 i l Rosin derivatives, parts by weight 100 100. i Rosin derivatives Flexalyn. Aldehydes, parts by weight. 5. Aldehydes Paraiormaldehyde. Metal compounds, parts by weight. 51 41. Metal compounds GO(CI SOQ)l'4 IO---- Co(C:HsO:):-4H:O.... Co(CiH;O,),-4H 0. Reaction time, hours 2. 2. Maximum reaction temperature, C 240 280.. 280. Color grade B1ue.. Blue. Blue. Melting point, ring and bell, C. Elastic fl 113. Time in hours to dissolve 20% solids in 2 2 l6 petroleum naphtha (B. P. 95-115 0.)

Example number 161 162 163 164 Rosin derivatives, parts by weight 100 100 100. Rosin derivatives Drying oil. Rosin oil. Aldehydes, parts by weight. 5. Aldehydes Paraformaldehyd Paraiormaldehyde. Metal compounds, parts by weig 41 38. Metal pompounds ZD(CIHIOI)Z'2H10- Reaction time, hours 3. Maximum reaction temperature, C. 250. Color grade B. Melting point, ring and ball, C. liquid. Time in hours to dissolve so 1 in 2. petroleum naphtha (B. P. -115 0.).

Example number 165 166 167 168 Rosin derivatives, parts by Weight 100. Rosin derivatives Methyl abietate. Aldehydes, parts by weight. 5 5. Aldehydes Perat'ormaldehyde. Paraiormaldehyde. Metal compounds, parts by weight... 41. Metal compounds ZIl(CzH301)r2HzO- M11(C2H302)2-4H10. Reaction time, hours 4 2. Maximum reaction temperature, C 250. Color grade B liquid Melting point, ring and ball, C liquid Time in hours to dissolve 20% solids in petroleum naphtha (B. P. 95115 0.).

Example number 172 Rosin derivatives, parts by weight 100. Rosin derivatives Ester gum. Aldehydes, parts by weight. 5. Aldehydes Paraformaldehydc. Metal compounds, parts by weight" 38. Metal COIIIDOUIldS MIKCaHaOflz-HLO. Reaction time, hours 3. Maximum reaction temperature, 260. Color grade D. Meltinilpoint, ring and ball, C 138. Time hours to dissolve 20% solids in 3.

petroleum naphtha (B. P. 95115 0.).

Example number 173 174 175 Rosin derivatives, parts by weight 100-. 100. Rosin derivatives Drying oil... Drying oil. Aldehydes, parts by weight 6 Aldehydes Paraformaldehyde. Paraiormaldehyde. Metal compounds, parts by weight 38 47. Metal compounds M!1(C:H;OI)2-4H:O.... Pb(C:H10:)z-3HzO. Reaction time, hours 2..-. 2. Maximum reaction temperature, C 250. Color grade Melting point, ring and .ball, C Time in hours to dissolve 20% solids in petroleum naphtha (B. P. 1.

The rosin drying oil used in Examples 162, 167, 173, and 175 was Flexalyn is a trade name used for the diethylene glycol ester 0 The ester gum used in the examples above had an acid number of rosin.

The rosin oil used in the examples above had an acid number of 7.

dashes in Examples 176 and 177 indiwte the melting points were not obtained.

prepared by the method outlined in U. S. Patent 2,429,264. I

- Table 9-Oontinued METAL BESINATES PREPARED FROM BOSIN DEBIV ATIVESContinued E t L 176 177 178 Rosin derivatives, parts by w 100 10o. Rosin.dciarivativeai).. glosin oll gall oil.

arts we fii geg. y Paraiormaldehyde. 4o goaraiormaldehyde.

M322 e g u fidiffi pmoimom-amouu rmcimoeramow rbwimoetamo. Reaction t e, hours i 4 Maximum reaction temperature, C 250 250 80. Color grade B B B. Melt point, ring and bell, C. mild Liquid. Time hcours to dissolve 20% solids in petroleum naphtha (B. P. 2 1 }6.

'lhe ester gum used in' the example abovehad an acid number of 9. The rosin oil used in the example above had an acid number of 7. The dashes in Examples 175 and 177 indicate the melting points were not obtained.

EXAMPLES 179-180 metal resinates had the characteristics shown in 1 One hundred parts of WW gum rosin and 5 Table 0 Table Example numberz. 179 180 Rosin, parts by weight- 100 100. Aldehydes, parts by weight 5 5. Aldeh des Para-n-butyraldehyde. Para-n-butyraldehydo. Parts y weight of metal compound required to block 13 23. Addiitlg81 metal compound added after H180 parts by 48 18.

we g Metal compounds Co(OiHr0:):4H:O...- Mn(C=HiO),4H,O. Reaction time, hours 6".-. 6. Maximum reaction temperature, C 275 260. Color grade Blue F. Melting point, ring and ball. C- 110 150. Time in hours to d'ssolve solids in petroleum naphtha 1% 2.

(B. P. 95-115 C.)

EXAMPLES 183-196 One hundred parts of WW gum rosin were heated to about C. with 0.01 part paraformaldehyde, without agitation. Agitation was commenced and the temperature raised to about 230 C. Metal compounds in the amounts and types indicated were reacted as the temperature was raised slowly to that temperature listed in the table following. After the times indicated, the products had the characteristics as listed in Table 12.

Table 12 METAL RESINATES PREPARED USING 0.01% FORMALDEHYDE-MODIFIED ROSIN Examplecnumber 183 184 185 186 Rosin, parts by weight 100. Paralormaldehyde, parts by wei ht.. 0.01. Metal compounds, parts by weig t... 35. Metal compounds 2PbC0;Pb(OH);. Reaction time, hours 2. Maximum reaction temperature, "C 260. Color grade H. Melting point, ring and ball, C Time in hours to dissolve 20% solids in petroleum naphtha 2.

(B. P. 95-115" C.)

Example number 187 188 189 190 191 Rosin, parts by weight 100. Paraiormaldehyde, parts by weight 0. 01. Metal compounds, parts by weight. 16. 7. Metal compounds Al(0H)(C;H1O1)1, Raction time, hours. 2. Maximum reaction temperature, 0-. 305. Color grade F WW B Green D. Melting point, ring and ball, "C over 170 over 17 07 143 over 160. Time in hours to dissolve 20% solids Soluble in 11.0-.-. 3,alcoholpreaent.... M M 1, little ppt.

in petroleum naphtha (B. P. 95-l15 C.)

The dashes in Example! 186 and 195 indicate the melting points were not obtained.

33 34 Table 12Contlnued METAL RESINA'IES PREPARED USING 0.01% FORMALDEHYDE-MODIFIED ROSIN-Continllod Example number 192 l 193 l 194 1 195 196 1 Rosin, parts by weight 100 100.

Paralormaldehyde. parts by weight 0. 01.

Metal compounds, parts by weight 6 36.

Metal compounds... Cerium salt.

Reaction time, hours 3.

Maximum reaction temperatur 200.

Color grade... B.

Melting int, 97.

Time in ours to dissolve 20% solids in petroleum $5.

naphtha (B. P. 95115 0.)

1 Examples 192, 193, and 194 were slurried in acetic acid. Example 196 was run same as Example 57. The dashes in Examples 186 and 195 indicate the melting points were not obtained.

EXAMPLE 197 added. After the rosln-paraformaldehyde had One hundred parts of WW gum rosin and reacted, the temperature was increased to that v 0.01% of paraiormaldehyde were heated .to 130 as listed in the table below. Metal compounds in C. without agitation. Agitation was commenced the amount and types were added, and the mixand the product allowed to cool to 80 C. ture stirred for the times indicated. The prod- Twenty-flve parts of copper acetate were added ucts had the characteristics as listed in Table 13.

Table 13 METAL RESINATES PREPARED USING FORMALDEHYDE-MODIFI'ED ROBIN Example number 198 199 200 201 202 Rosin, parts by weight Paraformaldehydc, parts by weight. Metal compounds, parts by weight. 25 8. Metal compounds Reaction time, hours 3 16.7. ZAI(OH)(CIHIOI)I- Magmum reaction temperature,

Color grade D. Melting point, ring and ball, C. over 160. Time in hours to dissolve 20% M.

solids in petroleum naphtha (B. P. 95l15 0.).

Example number 203 204 i 205 3 206 i 207 20a 4 Rosin, parts by weight Paralormaldehyde, parts by weight" Metal compounds, parts by weight. Metal compounds Reaction time, hours Maximum reaction temperature, O Color grade Melting point, ring and ball, "0 Time in hours to dissolve 20% solids in petroleum naphtha (B. P. 95-115 C.).

53c compound.

1 A little alcohol is necessary for complete solution. 7 The metal compounds used in Examples 204, 205, and 206, were slurried in acetic acid before adding. Example 207 used a solution as described in Example 63.

, 4 Example 208 used a cerium compound prepared as in Example 51.

slowly and the agitation continued. After 3 EXAMPLES 209-224 hours, the product was a clear green and took 10 o hundred parts by weight f ww gum rosin minutes to dissolve Solids in Petroleum and formaldehyde in the amounts and types as phtha. listed in the table following, were heated to about EXAMPLES 198-208, 170 C. without agitation. Agitation was commenced and the temperature was raised to about One hundred parts of WW gum rosin were 230 C. Metal compounds in the amounts and heated to about 130 C. with 5 parts of paraformtypes indicated were reacted as the temperature aldehyde without agitation. Agitation was comwas increased, as listed below. The products had menced and 25 parts of paraformaldehyde were 00 the characteristics listed in Table 14.

Table 14 METAL RESINAIES PREPARED USING DIFFERENT ALDEHYDE YIELDING MATERIALS Example number 209 210 211 212 Rosin, parts by weight 100 100 100.

Formaldehyde. parts by weight 5 2 6.

Type formaldehyde Trloxymethylene Hexamethylenetetra- Aqueous.

mine.

Metal compounds, parts by weight 38 38 38 41.

Reaction time, hours 3 2 3 3.

Maximum reaction temperature, C. 280 250- Melting point, ring and ball, C. 157 150.

(olor grade B D F.

Time in hours to dissolve 20% solids in incompletely sol Incompletely sol 8.

petroleum naphtha (B. P. 115 0.).

flli'ioxymethylene used was Du Pont's Trioxane.

Table 14-Continued METAL nasma'ras PREPARED USING DIFFERENT ALDEHYDE YIELDING MATERIALS-Continued Example number v 213 214 215 216 Rosi 11, parts by weight 10o 100-. 100 10o. Formaldehyde parts by wei 5. 1. a g Type formaldehyde 'Irioxymethylene Hexia methylenetetra- Gas Aqueous.

m e. Metal compounds parts by weight. 41 41... I 41 41.- Metal compounds: (Ci aO:):-4H:0--.. 0(C:Ha0:)r-4H:O.--. C0(C:HaO:)s-4H:O. C0(CzHa0a)3-4Ha0. Reaction time, hours 2 2..... 2. 4. Maximum reaction tern rature, 275 260 270 Melting point, ring and all, C 14 146 122. Color grade Blue..-. Blue. Time in hours to dissolve 20% solids in 1 1 petroleum naphtha (B. P. 95-115" 0.).

Example number 217 218 219 220 Rosin, parts by weight 100 100 100 100. Formaldehyde parts by weight. 4 5 5 12. Type formaldehyde Aqueous" TrioxymethyleneL Hexamethylene- Gas.

e ramme.

Metal compounds, parts by weight Metal compounds Reaction time, hours Maximum reaction temperature, C. Melting point, ring and ball, O... Color grade Time in hours to dissolve solids in petroleum naphtha (B. P. 95-115 0.

Example number I 221 Rosin, parts byweigh 100 t Formaldehyde parts by weight-.- 4 Type formaldehyde Aqueous Metal compounds, parts by weight Metal compounds Reaction time, hours Maximum reaction temperature, C

Melting point, ring and ball, "0

e Time in hours to dissolve 20% solids in petroleum naphtha (B. P. 95115 0.).

5. Gas.

ZPbCOa-PKKOH) 250.

1 Trioxymethylene used was Du Ponts 'lrioxane.

The dashes in Examples 221-224 indicate the melting points were not obtained on these metal reainates.

EXAMPLES 225-228 Five hundred parts of WW gum rosin and 150 parts of paraformaldehyde were heated to 200 C. with agitation in a pressure bomb for 3 hours. One hundred parts of this rosin-formaldehyde product were heated to about 230 C. with agitation. Metal compounds in the amounts and types indicated were reacted as the temperature was increased. After the times listed, the product had the characteristics listed in Table 15.

EXAIVIPLES 229-232 One hundred parts of WW gum rosin were heated to about 170 C. with the amounts of paratormaldehyde as indicated in the table below without agitation. Agitation was commenced and parts of manganese acetate were added as the temperature was raised as listed in the following table. After from 2 to 3 hours, the prod- Table 16 MANGANESE RESINATES PREPARED USING FORMALDEHYDE-MODIFIED ROSIN Example number 229 230 231 232 Rosin, parts by weight I 100 100 Paraformaldehyde, parts by weight. 1 2 4 EXAMPLES 233-240 One hundred parts of WW gum rosin and aldehydes in the amounts indicated in the following table were heated to about C. without agitation. The agitation was commenced and the temperature was increased to 230 C. Forty-one parts of manganese acetate [Mn(C:HaO2)2-4H:O] were ucts had the characteristics as indicated in 60 Table 16. added slowly as the temperature was increased to Table 1 5 Example number 225 226 227 228 Rosin, formaldehyde product, parts by weight, 100. containing 30% formaldehyde. 'Metal compounds, parts by weight 40. Metal compound 2PbCO;Pb(OH):. Reaction time, hours 1. Maximum reaction tempera 245. Color gra e B. Melting point, fine and ball, 4

The dash in Example 228 indicates the melting point was not obtained.

38 parts 01 manganese acetate [Mn(CzH3O2) z-4Hz0] were added slowly as the temperature was increased to 275 C. After 6 hours reaction time Table 17 MANGANESE RESINATES PREPARED USING ALDEHYDE-MODIFIED ROSIN Example number 233 234 235 236 237 238 239 240 Rosin, parts by weight 100 100 100. Aldehydes,partsbyweight. l 3 0.1. Aldehydes 2-etllylllvhgx- Paraldehydc.. Paraldehyde.. Paraldehyde.

a e y e. Manganese acetate, parts by 41 41 4i 41.

weight. Total reaction time. hours.. 5 5. Maximum reaction tempera- 275 275 275.

ure Melting point, ring and 150 149 141.

ball, C. Color grade G G G. Solubility, time in hours to 8 6 8.

dissolve 20% solids in petroleum naphtha (B. P. 95-l15 0.).

EXAMPLES 241.243

Mixed rosin and rosin derivatives in the amounts and types indicated were heated to about 170 C. with 5 parts of paraformaldehyde the resinate had a color grade of I, melting point of 145 0., ring and ball, and required 5 hours to dissolve 20% solids in petroleum naphtha (B. P.

EXAIMPLE 248 One hundred parts of WW gum rosin, one part of methyl abietate, and 5 parts of paraformaldehyde were heated to about 170 C. without agita- Table 18 MANGANESE RESINATES USING MIXED ROSIN MATERIALS Example number 241 242 243 Rosin, (parts by weight 50 100.

Rosin erivative, parts by weight 1.

Type rosin derivative methyl rosinate. Paraiormaldchyde, parts by weight 5 5.

Manganese acetate, parts by weight... Total reaction time, hours Maximum reaction temperature, C.. Melting point, ring and ball, C Color rade Solubility, time in hours to naphtha (B. P. 95-115 C EXAMPLES 244-246 Table 19 MANGANESE RESINATFS PREPARED USING MAJIGANESE COMPOUNDS Example number I 244 I 245 I 246 Rosin, parts by weight 100 100 100. Paraiormaldehyde, parts by weight 5 5 5.

Manganese compounds, parts by weight 20' l0 18.5. Type manganese compound MnClr. MnOz... MnCO: Total reaction time, hours 4 l 3. Maximum reaction temperature, C 300 280.. 280. Melting point, ring and ball, C liquid... over 200 164. Solubility time in hours to dissolve 20% solids in petroleum naphtha (B. P. 95-115 C.) H2 3 5.

l Part of the manganese chloride added did not react.

EXAMPLE 247 One hundred parts of WW gum rosin, 2.5 parts of propionaldehyde. and 2.5 parts of isobutyraldehyde were heated to about 170 C. without agitation. The agitation was commenced and the temperature was increased to 230 C. Forty-one EXAMPLE 249 One hundred parts of WW gum rosin, 38 parts of manganese acetate, and 5 parts of paraformaldehyde were heated altogether to about 170 C.

-without agitation. Agitation was commenced and the temperature was raised to about 230 C. The product was poured after 1 hours reaction time and had a color grade of I. M. P. 161 0., ring and ball, and was soluble in petroleum naphtha and turpentine.

EXAMPLE 250 One hundred parts of WW gum rosin were heated to about 170 C. without agitation. Agitation was commenced and the temperature was raised to about 230 C. Manganese acetate was added until the material blocked. This occurred at 16.0 parts of manganese actate at a temperature of 260 C. The temperature was raised and additional manganese acetate added until the Fiity parts of WW gum rosin, fifty parts of I methyl abietate, and parts of paraldehyde were heated to about 170 C. without agitation. Agitation was commenced and the temperature was raised to 230 C. Forty-one parts of were added slowly as the temperature was raised to 250 C. After a total reduction time of 5 hours, a clear soluble resin with a color grade of E and'a melting point (ring and ball) of 158 C. was obtained. Two grams of this resin completely dissolved in 10. grams of petroleum naphtha after shaking for 7 hours.

EXAMPLE 252 One hundred parts of WW gum rosin and 5 parts of dihydropyran were heated to about 170 C. without agitation. Agitation was commenced and the temperature was increased to 230 C. Thirty-eight parts of manganese acetate [MII(C2H3O2)2'4H2O] were added slowly as the temperature was increased to 250 C. After 2 hours reaction time the product had a color grade of N, melting point of 157 C., ring and ball, and required 8 hours to dissolve in petroleum naphtha (B. P. 95-115" C.)

EXANIPLE 253 One hundred parts of WW gum rosin and 5 parts of paraformaldehyde were heated to about 170 C. without agitation. Agitation was commenced and the temperature was increased to 250 C. Thirty-five parts of manganese acetate [Mn(CzH:O2)2'4I-I2O] and 2 parts of manganese.

carbonate [MnCOa] were added slowly as the temperature was increased to 300 C. After 4 hours, the product was a clear, homogeneous resin. In order todetermine the maximum temperature at which this resinate could be heated without noticeable decomposition, the temperature was raised to 350 C. for 1 hour and further increased to 380 C. and held at this temperature for 1.5 hours. tion had occurred during the previous heating, the temperature was raised to 400 C. and held at this point for hour. Only a small amount of volatile oil distilled during this heating. The product had a melting point of 122 C. ring and ball. Only a slight precipitate separated out upon dissolving the resin (20% solids) in petroleum naphtha (B. P. 95115 C.).

EXAMPLE 254 Three hundred parts of WW gum rosin and 88.6 parts of paraldehyde were charged in a pres- Since no appreciable decomposisure bomb and the temperature raised to 200 C.

After 4 hours agitation the bomb was allowed to cool to room temperature. The product from the reaction was dissolved in petroleum naphtha and the unreacted aldehyde and naphtha removed by steam distillation. The resulting rosinpgmlaldehyde reaction product had a color grade 0 One hundred parts of the above product were "heated to about 170 C. without agitation. The

agitation was commenced and the temperature raised to 260 C. Thirty-nine parts of manganese acetate were added slowly over a period of 4 hours. The heating and agitation were continued for a total of 4 hours. The product had a color grade of D, melting point 148 C. ring and ball, and required 6 hours to dissolve solids) in petroleum naphtha (B. P. 95-115 C.). EXAMPLE 255 Five hundred parts of WW gum rosin and 500 parts of heat bodied linseed oil were heated at 75 C. with agitation for 4 hours. Six hundred parts of turpentine were added and this varnish stock solution was allowed to cool to room temperature.

A turpentine solution of the manganese resinate from Example 21 was prepared. A sufllcient quantity of this solution was added to 100 parts of the varnish stock solution to give the drier concentration shown in Table 20. The efiect of using this manganese resinate as a drier in cona junction with cobalt and lead driers was also checked. The varnish containing the drier was then diluted to a D viscosity on the Gardner- Holdt scale.

Glass test plates were prepared by dipping 3 x 5 glass plates in the varnish solution and allowing them to stand at a angle for the times indicated in the following table.

Table 20 EVALUATION OF ALDEHYDE-MODIFIED MANGANESE RESINATES AS DRIERS Time Bward Drier Gramsmetal/lOOgramsstocksolutron hours Hardnesa None None 06 0 Mn 16 24 16 Mn 0.16" 72 22 M11 0.16 96 26 Co-Pb-Mn 0.05Co-0.05Pb-0.05Mn 72 26 Co-Ib 0.08Co-0.08Pb 72 16 EXAMPLES 256-260 Table 21 Example number 256 257 258 250 260 Rosin-parts b weight 100 100 100 100 100 Paraformalde yde, parts b weight. 5 5 5 5 10 Cobalt salts, parts by weig t 25.3 18.0 16.0 40 50.6 Type cobalt salts C010; C000; 00(011); 00,0; 00 0; Total reaction time. how-3.... 2 2 1 3 4 Maximum reaction temp., C. 270 270 290 300 300 Melting Eoint, C. (ring and ball) 118 117 over 200 75 76 Time in ours to dissolve 40% solids 1 1 1 94 l )6 inpetroieumnaphtha (05-1 15 C.)

i Slight ppt. 

1. A PROCESS OF PREPARING A REFUSIBLE METAL RESINATE PRODUCT SOLUBLE IN PETROLEUM NAPHTHA, COMPRISING: FUSING 100 PARTS OF A ROSIN MATERIAL: 0.01 TO 30 PARTS OF FORMALDEHYDE EQUIVALENT OF A FORMALDEHYDE YIELDING MATERIAL; AND A REACTIVE METAL MATERIAL WHICH YIELDS ITS METAL TO THE ROSIN-FORMALDEHYDE REACTION PRODUCT UNDER THE CONDITIONS OF THE REACTION, AT A TEMPERATURE BELOW THE DECOMPOSITION TEMPERATURE OF THE METAL RESINATE, BEING IN THE RANGE 90* C. TO 400* C., THE METAL MATERIAL BEING TAKEN FROM THE GROUP CONSISTING OF THE FREE METAL, THE METAL OXIDE, HYDROXIDE, CARBONATES, AND THE METAL SALTS OF ORGANIC CARBOXYLIC ACIDS. 